Addition of methane during microwave coal pyrolysis could greatly affect the product distribution to valuable products including the formation of char. Here in this work, low rank coal was exposed to microwave energy in the presence of different methane concentrations (0, 25, 50, and 90%) at 980 �C for 2 h. Increasing methane concentration was found to increase both the char and tar yields mainly due to carbon deposition during methane decomposition and hydrogenation of trapped carbon into tars. Analysis of the gas composition suggested that some of the methane was activated in the presence of the coal minerals, which could act as a catalyst, forming light hydrocarbons C<
sub>
2<
/sub>
?C<
sub>
7<
/sub>
which account for up to 5% of the gaseous products at a methane concentration of 90%
they accounted for less than 0.5% in the absence of methane. Methyl groups may also have been substituted into aromatic compounds as observed in the tar analysis where the number of methyl substitutions in the detected parent phenol and naphthalene increased with methane concentration. Tar yield could also increase indirectly with methane addition through hydrogenation reactions with unsaturated coal compounds. The formation of char under different methane concentrations was examined by many characterization tools including Raman, dielectric properties, XRD, BET, SEM, and EDS. The results suggest that the addition of methane did not help in forming ordered carbon chars, not only due to amorphous carbon deposition on the char surface but also due to hydrogenation or alkylation reactions with char. The presence of methane enhanced the formation of C<
sub>
2<
/sub>
s and benzene
a possible correlation between the formation rate of benzene and hydrogen during pyrolysis is proposed.